Certificate of correction



2,856,528 Patented Sept. 2, i958 oRGANomrALLrc COMPOUNDS Rex D.- Closson, Northville, MiclL, assignor to Ethyl I Corporation, New York, N. Y., a corporation of Del- "aware.

' I Nb Drawing. Application June 21, 1954 Serial No. 438,357

Claims. (Cl. 260-541) This invention relates to novel compositions of matter and in particular to novel organometallic compounds in which the 'a-carbon atom of a metal salt of an organic acid is substituted with a metal.

Certain tan-metallic substituted organic salts have been seltiorth in the literature. -In. particular, OL-SOdlO-SOdiUmmine. particular characteristics of these compounds ex- 1 cept for their probable formation as intermediates in the preparationof the substituted malonic acids. In addition, other workers have suggested the formation of asodio-ethylacetate by the reaction of triphenylmethyl sodium with ethyl acetate. These prior art compounds have .the particular disadvantage of being unstable under atmospheric conditions and at elevated temperatures. As a result of my work in this field, I have discovered novel compositions of matter which possess unexpected stabiljity and are of particular benefit to the art as a basic raw material in the preparation of various chemicals.

It-is an object of the present invention to provide new and novel compositions of matter. A particular object is to' provide a-metallo-metallic salts of organic acids, particularly acetic acid. A still more specific object of thisyinvention is to provide the novel composition asodio-sodium acetate. These and other objects will be apparent as the discussion proceeds.

The above and other objects are accomplished by providing novel ot-metallo-metallic salts of organic acids. The novel products I especially prefer are theu-metallometallic acetates. Thus, these compounds are compounds in which the ionic structure is satisfied by mono or polyvalent metallic ions. My

novel compositions can be depicted by the formula M: CHz-C wherein M and M' can be the same or different and are valent elements, particularly the alkali and alkaline earth metals, especially sodium. Thus, a particularly preferred compound of my invention is ot-sodio-sodium acetate In certain instances, one or both of the remaining hydrogen atoms on the a-carbon atom can be substituted with lower alkyl radicals, especially those having 3 carbon atoms or less, and these compounds will likewise exhibit the superior characteristics of the structure containing only 2 carbon atoms.

The novel compositions of myinvention have the characteristic of 'being stable under atmospheric conditions and at elevated temperatures, especially the m-sodio-sodium acetate. acetates surprisingly is superior to that of the u-sodiosodium caproate and the ot-sodio-ethyl acetate compounds of the prior art.

salts essentially free of other organometallic compounds which cannot be readily separated therefrom and hinder, by competing reactions, many processes in which they can be employed. Consequently, my compounds are of considerably more utility in various reactions and in fact can be handled in air without the danger of rapid decomposition. caused by moisture in air, although this hydrolysis is quite slow.

The following examples describe methods of preparing my compounds and certain physical characteristics.

Example I To a container flushed withnitrogen was added 7.8 parts of finely divided sodium amide and 24.6 parts of finely divided anhydrous sodium acetate. The mixture was agitated in order to obtain a uniform distribution of particles. From the container the mixturewas fed intermittently over a period of vone hour to a reaction vessel previously heated to a temperature of about C. which was also flushed with nitrogen. The reaction vessel was equipped with means for agitation and inlet andoutlet ports. The feed to the vessel was such that the temperature was maintained between 180 and 235 C. and the reaction mixture was continuously agitated. Am-v monia was evolved. The ammonia was absorbed in a 2 N solution of hydrogen chloride. At the completion of the addition to the reactor, the ammonia evolution had essentially ceased and the heat was removed. The product a-sodio-sodium acetate, free of other organometallic compounds, remained in the reaction vessel and wasjrecovered therefrom. Titration of the hydrogen chloride solution indicated a yield of product of 89.5% based on the sodium amide.

Example 11 ployed, and the temperature varied between 173 to 240 C. The total reaction time was 40 minutes. Determina tion of the amount of ammonia absorbed in the hydrogen chloride solution indicated a yield of greater than 99% based on the sodium amide. The product remaining in the reaction vessel was white and did not decompose upon heating to 375 C.

To establish the identity of the product, 38.6 parts of n-octyl bromide were added to the product obtained in Example II, and about 50 parts of n-nonane were added as a diluent to the mixture. This mixture was refluxed for about 6 hours and solids which formed were filtered oil. The solid product was dissolved in water and acidified. A yellow oil then separated which was extracted with ether three times. A yellow product, decanoic acid, was recovered by evaporating the ether therefrom. This The stability of the a-metallo-metallic' Another particular I advantage of this invention is that it provides ot-metallo-metallic organic Some hydrolysis of my compounds product melted at about 27 C., whereas decanoic acid melts at 31 C. A portion of this acid was treated with thionyl chloride and then with aniline in benzene solution. The solid material obtained after removal of the benzene was 'recrystallized and found to have amelting point of 61:5 to.62.5 C., whereas the meltingpoint of-the anilide of decanoic acid is reported to be 6200. Asecond'portion of the acidwas treated with an excess of 'thionyl chloride and then with'anhydrous ammonia in benzene solution. The ammonium chloride was removed by filtration and the benzene evaporated. The crystalline product remaining was twice recrystallized from methanol. The resulting product had a meltingpoint between 97.2 and'98.4 0., whereas themelting point of capric amide isreported in the literature as being 98 C. Thus, it

has: been established. that oc-SOdiO-sOdillm acetate was prepared.

Example Ill m-Lithio-sodium acetate is prepared by reacting essen= tially stoichiometric quantities of lithium amide with'anhydrous sodium acetate.

Example IV mSodio-potassium acetate is prepared by reacting anhydrous potassium acetate with sodium amide essentially as described in Example I at atemperature of about 250 C. Reaction proceeds smoothly to produce the product in good yield and purity.

Example V a-Sodio-zinc acetate is prepared in good yield by 'reacting sodium amide-with anhydrous zincacetate according to the procedure of Example I.

Example Vl When zinc amide is reacted with dehydratedlead acetate, essentially as described in Example I, d-zinc-l'ead acetateis produced;

It will' be evident that other a-metallo-metallic salts can be prepared by using the appropriate starting materials. As pointed out above, I prefer the a-meta'llometallic compounds in which the metallic elements are alkali or alkaline earth metals as, for example, sodium, potassium, lithium, rubidium, cesium, calcium, barium, strontium, magnesium, and beryllium. Thus, among the'novel compositions of this invention are, for example, oa-lithiO-lithium acetate; a-lithio-sodium acetate; oc-lithiopotassium acetate; a-lithio-rubidium acetate; u-lithiocesium acetate; u-sodio-pOtaiSsium acetate; nc-SOdiO-l'llbidium acetate; a-sodio-cesium acetate; a-potassio-rubidi'um acetate; a-potassio-cesium acetate; a-rubidio-cesium acetate; u-potassio-potassium acetate; a-rubidio-rubidium acetate; a-cesio-cesium acetate; a-beryllio-beryllium acetate; a-beryllio-magnesium acetate; a-beryllio-calciumacetate; a-beryllio-strontium acetate; et-beryllio-barium acetate; a-magnesio-calcium acetate; u-magnesiowstrontium" acetate; a-magnesio-barium acetate; a-calcio-strontium acetate; oz-calcio-barinm acetate; et-strontio-bariumacee tate; a-magnesio-magnesium acetate; m-calcio-calcium ace:

tate; a-strontio-strontium acetate; and u-bari'o-barium acetate. Other-novel compositions of my invention'are a-sodio-beryllium acetate; a-sodio-magnesium acetate; asodio-calcium acetate; a-sodio-strontium acetate; and asodio-barium acetate. Likewise, compounds in which the other alkali metals-that is, lithium, potassium, etc., replace sodio in the latter examples, will be evident as being among my novel compositions. In addition, other novel compositions include, for example, ut-calcio-v sodium acetate and the like compounds in which the calcio is replaced with other alkaline earth metals and the sodium is replaced with other alkali metals/ The foregoing examples arethe compositions which I prefer. I especially prefer a-sodio-sodium acetate primarily because of the greater availability and reactivity of sodium.

Other compounds encompassed by this invention are, i

for example, u-sodio-aluminum acetate; wpotassiocadmium acetate; ot-calcio-cerous acetate; ,oc-lithlO-Chlfi,

uniquecharacteristic of .being stable; As pointed'out, u-sodio-s0diumac etate does not decompose even at tem-.

peratures aboveabout 375 C. Consequently, these unique-materials 'are: of particularbenefit to .the in. that" they provide a comparatively basic" chemical from: which various-compounds can be readily obtained. For

example; when-the compounds of this'inventionare' ree acted withorganic halides, the metallic salt'ofian organic acid is obtained which can be readily' converted. to the acid itself. I reacted with organic dihalides in order to produce, upon subsequent hydrolysis, various dibasic acids -whick find:

particular utility in the art as, forexample," in the formationof various polymeric materials. uses w-ill'b'e evident to those skilled intheartr Having thus described the novel compositions of myin vention; what Iclaim is:-

1. A -stable' whitesolid which is an alpha-metallo-me tallic acetate essentially freeof other" organo-metallic" compounds and containing two carbonatoms wherein the alpha-metallo element is selected from 'thegroup con sisting of alkali metals, alkalineearthmetals=-andfzinc.-

2. As;- compositions of matter, stable a-metallo-mee tallicracetates' containing two carbon atoms whereinthealpha-metallo element is an alkaline-earth-metal.-

3. The combination-of claim 1 in which the-a-metalloelement-is an alkali metal. a

4. A stable-white solid which is alpha-sodiosodiunr acetate: essentially free of. other. organometallic compounds.

5. The composition of -claim-l wherein -the'--othermetallic element is selected from the group consisting of alkaline earth metals, cerium, zinc and lead.

No references cited.

Likewise, these 'novel compositions can be;

These andf'other UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noa 2,850,528 September 2, 1958 Rex: D0 Closson It is herebf; certified that error appears in the -printed specification of the above "numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line '7, for "620 0," read 62 0., column .4, line 61, strike out "No references cited."

and under the heading OTHER REFERENCES insert Morton et alas J A Go S vol, 60, pages l426=9 (1938) Signed and sealed this 16th day of December 1958.,

SEAL fittest KARL Ho AXLINE Attesting Oificer ROBERT C. WATSON Commissioner of Patents ENTTEE STATES PATENT oEETcE (JE'iIIHQAiE @F 'QQRECTION Patent Noa 2,859,528 September 2, 1958 Rex Du Closson It is hereby certified that error appears in the -printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line '7, for "620 C0" read m 62 C. column .4, line 61,

strike out No references citeda" and under the heading OTHER REFERENCES insert Morton et e10: 31A, Co Sq, volo 60, pages l426=9 (1938) en EAL l testz KARL Ha AXLINE Attesting Oificer ROBERT C. WATSON Commissioner of Patents 

1. A STABLE WHITE SOLID WHICH IS AN ALPHA-METALLO-METALLIC ACETATE ESSENTIALLLY FREE OF OTHER ORGANO-METALLIC COMPOUNDS AND CONTAINING TWO CARBON ATOMS WHEREIN THE ALPHA-METALLO ELEMENT IS SELECTED FROM THE GROUP CONSISTING OF ALKALI METALS, ALKALINE EARTH METALS AND ZINC. 